Air Quality Measurements from the Fresno Supersite

ABSTRACT

The Fresno Supersite intends to 1) evaluate non-routine monitoring methods, establishing their comparability with existing methods and their applicability to air quality planning, exposure assessment, and health effects studies; 2) provide a better understanding of aerosol characteristics, behavior, and sources to assist regulatory agencies in developing standards and strategies that protect public health; and 3) support studies that evaluate relationships between aerosol properties, co-factors, and observed health end-points. Supersite observables include in-situ, continuous, short-duration measurements of 1) PM_2.5, PM₁₀, and coarse (PM₁₀ minus PM_2.5) mass; 2) PM_2.5 SO₄ ^-2, NO₃ ^-, carbon, light absorption, and light extinction; 3) numbers of particles in discrete size bins ranging from 0.01 to ~10μm; 4) criteria pollutant gases (O₃, CO, NO_x); 5) reactive gases (NO₂, NO_y, HNO₃, peroxyacetyl nitrate [PAN], NH₃); and 6) single particle characterization by time-of-flight mass spectrometry. Field sampling and laboratory analysis are applied for gaseous and particulate organic compounds (light hydrocarbons, heavy hydrocarbons, carbonyls, polycyclic aromatic hydrocarbons [PAH], and other semi-volatiles), and PM_2.5 mass, elements, ions, and carbon. Observables common to other Supersites are 1) daily PM_2.5 24-hr average mass with Federal Reference Method (FRM) samplers; 2) continuous hourly and 5-min average PM_2.5 and PM₁₀ mass with beta attenuation monitors (BAM) and tapered element oscillating microbalances (TEOM); 3) PM_2.5 chemical specia-tion with a U.S. Environmental Protection Agency (EPA) speciation monitor and protocol; 4) coarse particle mass by dichotomous sampler and difference between PM₁₀ and PM_2.5 BAM and TEOM measurements; 5) coarse particle chemical composition; and 6) high sensitivity and time resolution scalar and vector wind speed, wind direction, temperature, relative humidity, barometric pressure, and solar radiation. The Fresno Supersite is coordinated with health and toxicological studies that will use these data in establishing relationships with asthma, other respiratory disease, and cardiovascular changes in human and animal subjects.     

Redundant Measurements of Urban Air Monitoring Networks in Air Quality Reporting

Abstract

This paper describes a statistical method to assess site redundancy of urban air monitoring networks in reporting daily Pollutant Standards Index (PSI), average concentrations, and the number of exceedances. Such a statistical method has identified significant redundancy in monitoring sites for one-year measurements of two air monitoring networks in Taiwan. There are five redundant sites out of 15 monitoring sites in the Taipei area and eight redundant sites out of 18 monitoring sites in the Kaohsiung area. By using the statistical method presented in this paper to downsize the monitoring networks, we can determine not only the number of redundant sites but also the priority of site removals. The derived sub-networks can maintain consistency in reporting air quality without significant changes in the spatial variations of air measurements for an existing air monitoring network.     

Extinction Measurements for Sensitive Assessment of Air Quality

Measures of horizontal extinction were initiated at the Lowell Observatory at Flagstaff, Arizona In January of 1972, and by October of 1973 an instrumental accuracy compatible with the best observing conditions was achieved. Excellent data obtained in a horizontal direction during a seven night run are compared with long term highly standardized astronomical measures of extinction obtained at Flagstaff during the period 1955–1972. The data obtained both vertically and horizontally suggest that the extinction and scattering due to aerosols were at times as low as 10% of that caused by molecular (Rayleigh) scattering alone. The vertical extinction seems to correspond (with several months lag) to rough estimates of volcanic loading; the effect of the March 17, 1963 outburst of Mount Agung, a volcano on the island of Bali, very probably caused abnormally high extinction in late summer of that year. A generally high extinction level was observed throughout 1964-1965 with a rather slow decay to a “normal” level showing up by 1966. The very high level of transparency and abnormally blue sky found in 1961 was again observed in 1972. These data strongly suggest that man-made aerosols are not yet the major contributor to the particulate matter in the upper atmosphere.     

Air Quality Measurements for the Aerosol Research and Inhalation Epidemiology Study

Abstract

Measurements of pollutant gases, airborne particulate matter mass and composition, and meteorology have been made at a core site near downtown Atlanta, GA, since August 1998 in support of the Aerosol Research and Inhalation Epidemiology Study (ARIES). This site is one of eight in the Southeastern Aerosol Research and Characterization network. The measurement objective is to provide a long-term, multivariate dataset suitable for investigating statistical associations of respiratory and cardiovascular disease with airborne particulate matter composition, meteorology, and copollutant gases through epidemiologic modeling. Measurements are expected to continue through 2010. Ancillary multiyear measurements at additional sites in the Atlanta metropolitan area and in short-term exposure assessments have been used to estimate the exposure/measurement error associated with using data from a central site to approximate human exposures for the entire area. To date, 13-, 25-, and 53-month air quality datasets have been used in epidemiologic analyses.     

A Method for Using Air Pollution Measurements and Public Opinion to Establish Ambient Air Quality Standards

Air quality was comprehensively evaluated by means of sampling at 21 locations over metropolitan Birmingham during a period of one year. Thousands of integrated samples of three common atmospheric gaseous pollutants and two common particulate pollutants were collected and analyzed. Following the year of sampling in 1964, a random household survey was completed by conducting personal interviews at more than 7200 households over metropolitan Birmingham. Statistical reduction of household survey results by census tract and by neighborhood area provided domestic fuel and waste burning emission data as well as public (resident) opinion on specific air pollution effects. The relationship between ambient air quality and neighborhood opinion of air pollution effects on health and property are evaluated statistically. Ambient standards are suggested which are based upon those air pollution levels shown to have adverse effects on approximately one-third of the people.     

Development of Instrumentation for Continuous On-line Monitoring of Non-Methane Organic Carbon in Air Emissions

ABSTRACT

Non-methane organic carbon (NMOC) is a measure of total organic carbon in an air emission, excluding that from methane. Thus, it measures the total amount of carbon, irrespective of the structure and functional groups in the molecule. The U.S. Environmental Protection Agency (EPA) Method 25 is used for quantification of NMOC in emission sources and in ambient air. This method involves laboratory analysis of collected air samples and cannot be used for real-time measurements. It is prone to interferences from CO₂, CH₄, and CO, as well as moisture. In this paper, a novel method for continuous, on-line monitoring of NMOC in air emissions and ambient air is presented. Detection limits are at ppb levels, and interference of permanent gases have been eliminated.     

Hydrocarbon Measurements During the 1992 Southern Oxidants Study Atlanta Intensive: Protocol and Quality Assurance

Abstract

A major component of the Southern Oxidants Study (SOS) 1992 Atlanta Intensive was the measurement of atmospheric nonmethane hydrocarbons. Ambient air samples were collected and analyzed by a network of strategically located automated gas chromatography (GC) systems (field systems). In addition, an extensive canister sampling network was deployed. Combined, more than 3000 chromatograms were recorded. The SOS science team targeted for quantitative analysis 56 compounds which may be substantial contributors to ozone formation or used as air mass tracers. A quality assurance program was instituted to ensure that good measurements were being made throughout the network for each target compound. Common, high-quality standards were used throughout the network. The performance of individual field systems was evaluated during the intensive through the analysis of challenge mixtures. This methodology helped to identify and correct analytical problems as they arose.     

Estimating Emissions from Air Concentration Measurements

A one-year-long experiment in which two different tracers were simultaneously released from two different locations was used to test various hybrid receptor modeling techniques to estimate the tracer emissions using the measured air concentrations and a meteorological model. Air concentrations were measured over an 8-hour averaging time at three sites 14 to 40 km downwind. When the model was used to estimate emissions at only one tracer source, 6 percent of the short-term (8-h) emission estimates were within a factor of 2 of the actual emissions. Temporal averaging of the 8-h data enhanced the precision of the estimate such that after 10 days 42 percent of the estimates were within a factor of 2 and after six months all of them (each source-receptor pair) were within a factor of 2. To test the ability of the model to separate two sources, both tracer sources were combined, and a multiple linear regression technique was used to determine the emissions from each source from a time series of air concentration measurements representing the sum of both tracers. In general, 50 percent of the short-term estimates were within a factor of 10, 25 percent were biased low, and in another 25 percent the regression technique failed. The bias and failures are attributed to low or no correlation between measured air concentrations and model calculated dispersion factors. In the regression method increased temporal averaging did not consistently improve the emission estimate since the ability of the model to distinguish emissions between sources was diminished with increased averaging time. However, including progressively longer time periods (more data) into the regression or spatially averaging the data over all the receptors was found to be the most effective method to improve the estimated emissions. At best about 75 percent of the estimated monthly emission data were within a factor of 10 of the measured values. This suggests that the usefulness of meteorological models and statistical methods to address questions of source attribution requires many data points to reduce the uncertainty in the emission estimates.     

Ambient Air Measurements of Petroleum Refinery Emissions

An ambient air monitoring program to characterize airborne emissions from the Exxon petroleum refinery at Benicia, California was conducted during September 8–22, 1975. Ground level sampling facilities and an instrumented aircraft provided an integrated, three-dimensional monitoring network. Measurements made during the study included ozone, oxides of nitrogen, methane, carbon monoxide, individual C₂-C₆ hydrocarbons, halocarbons, condensation nuclei, visual distance and various meteorological parameters. The study focused on three major areas: (1) the characterization of gaseous components within the refinery effluent, especially non-methane hydrocarbons and ozone, (2) natural sunlight bag irradiation experiments to determine the ozone forming potential of refinery emissions, and (3) an investigation of changes in plume chemistry as refinery emissions were transported downwind.     

Solar Radiation Measurements Augment Air Pollution Studies

For several years an ongoing project at the U. S. Water Conservation Laboratory has dealt with the measurement and analysis of solar radiation. Generally, this study has been directed toward fulfilling the needs of agriculture. As a byproduct, however, much has also been learned about the particulate matter content of the air, since the work involved has all been carried out within the metropolitan Phoenix, Ariz. area. In this paper, the results of several years of research on the atmospheric transmission of solar radiation in this area are presented. These results are considered in light of concurrent meteorological conditions, and inferences are drawn with respect to spatial and temporal variations in airborne particulates. It is demonstrated that solar radiation measurements can greatly enhance our knowledge of air pollution dynamics.     

Source Fingerprints for Volatile Non-Methane Hydrocarbons

Non-methane hydrocarbon (NMHC) source profiles consisting of 35 hydrocarbon species were measured for vehicle and petroleum refinery emissions. Refueling emissions were found to be sensitive to the grade and volatility class of fuel and to be composed mainly of saturated hydrocarbons such as n-butane and 2-methy I butane. Unsaturated and aromatic hydrocarbons, which are released from the tailpipe of vehicles as products of combustion and unburned fuel, were more prevalent in roadway emissions comprising approximately 34 percent of the total NMHCs. Cold-start emissions were nearly indistinguishable from the roadway emission profile. The only significant differences were in toluene, ethylene and acetylene, which may be related to the efficiency of combustion when the vehicle is initially started. Saturated hydrocarbon distributions of the hot-soak profiles were found to be similar to refueling emissions. The only significant difference in the profiles was in the aromatic content, which may be related to the grade of the gasoline and the effectiveness of evaporative emission control devices. The temporal variation in refinery emissions was significant and may be related to variations in refinery activities such as the production and blending of feed stocks to produce different fuels.     

Ozone Air Quality Models

Abstract

The field of ozone air quality modeling, or as it is commonly referred to, photochemical air quality modeling, has undergone rapid change in recent years. Improvements in model components, as well as in methods of interpreting model performance, have contributed to this change. Attendant with this rapid change has been a growing need for those developing and using air quality models and policy makers to have a common understanding of the use and role of models in the decision making process. This Critical Review highlights recent advances and continuing problem areas in photochemical air quality modeling. Emphasis is placed on the components and input data for such models, model performance evaluation, and the implications for their use in regulatory decisions.     

Measurements of Morbidity and Mortality Related to Air Pollution

Examination of total deaths in New York City by day of occurrence shows periodic peaks in mortality which are associated with periods of high air pollution. These peaks are usually associated with periods of low wind speed and temperature inversion conditions which permit air pollution to build up to high levels. Unlike the experience of London, fog is not a necessary part of this picture, and therefore the presence of these episodes is often not apparent at the time to most inhabitants. A characteristic feature of these episodes is the immediate rise in mortality occurring on the same day as the peaks of pollution. A second characteristic is their frequent influence on death rates in the 45–64 year age group as well as in those over 65. These characteristics suggest that if these excess deaths are related to air pollution (as we believe to be highly likely) the mechanism is probably protean and pervasive affecting the course of a variety of different diseases through a basic physiologic effect. The relationship of morbidity in a normal urban population to air pollution is also demonstrated by time series analysis of correlation coefficients. The relation of two symptoms (cough and eye irritation) in a group of 1090 persons observed for three years is compared with two measures of air pollution (SO₂ and particulate density) to which they were exposed. Time lags of up to 28 days were introduced and a constant relationship between air pollution levels and those symptoms was demonstrated.     

Simultaneous Total Oxidant and Chemiluminescent Ozone Measurements in Ambient Air

The purpose of this project was to investigate the relationship of ambient air quality measurements between two analytical methods, referred to as the total oxidant method and the chemiluminescent method. These two well documented analytical methods were run simultaneously, side by side, at a site on the Houston ship channel. They were calibrated daily. The hourly averages were analyzed by regression techniques and the confidence intervals were calculated for the regression lines. Confidence intervals for point estimates were also calculated. These methods were used with all data sets with values greater than 10 parts per billion and again with values greater than 30 parts per billion. A regression line was also calculated for a second set of data for the preceding year. These data were generated before a chromium triox-ide scrubber was installed to eliminate possible chemical interferences with the Kl method.

The results show that in general the chemiluminescent ozone method tends to produce values as much as two times higher than the simultaneous total oxidant values. In one set of data collected an 80 ppb chemiluminescent ozone value predicted a value of 43.9 ppb total oxidant with a 95% confidence interval of 7.7 to 80.4 ppb. In the second set of data an 80 ppb chemiluminescent ozone value predicted a value of 78 ppb total oxidant with a 95% confidence interval of 0.4 to 156 ppb. Other statistical analyses confirmed that either measurement was a very poor predictor of the other.     

Ambient Air Hydroxyl Radical Concentrations: Measurements and Model Predictions

This review critically examines the limited number of recent near surface measurements of hydroxyl radicals in urban and rural areas. Predictions of average tropospheric, hemispheric and/or zonal concentrations of hydroxyl radicals derived from methylchloroform and carbon monoxide concentrations and models are discussed. The limitations of one- and two-dimensional model predictions of zonal and seasonal hydroxyl concentrations receive detailed consideration. Of especial concern on a regional scale are cloud cover effects on the penetration of ultraviolet radiation below 320 μm which is critical to the subsequent reactions forming hydroxyl radicals.     

Air Quality Control Equipment Guarantees

The purpose of this paper is to discuss considerations regarding guarantees of air quality control equipment. Topics include specification design parameters to cover ranges of expected operating conditions, negotiation of performance guarantees, design changes during construction, reliability, performance testing and comparison of test conditions to the worst expected conditions for which the guarantees apply. Comments are also offered regarding corrective actions in event the guarantees are not complied with.